CN103364463A - pH sensor based on reduced graphene oxide (RGO) and pH value detection method using same - Google Patents
pH sensor based on reduced graphene oxide (RGO) and pH value detection method using same Download PDFInfo
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Abstract
The invention discloses a pH sensor based on reduced graphene oxide (RGO) and a manufacturing method thereof, and a pH value detection method using the sensor. The manufacturing method of the sensor comprises the following steps: directly synthesizing a graphene oxide film from a graphene oxide (GO) sheet, coating a silver (Ag) or gold (Au) layer on a silicon dioxide (SiO2)/silicon (Si) substrate by vacuum coating to obtain electrodes, transferring the previously synthesized graphene oxide film between the electrodes, and naturally drying in air at room temperature; putting the prepared sample into a reaction kettle, evacuating air with nitrogen, and reducing by heat treatment; and making a trench along the edge of the reduced graphene oxide film with PMMA (polymethyl methacrylate) or any other insulating polymer to constitute a complete device for detecting the pH value variations.
Description
Technical field
The detection method that the present invention relates to a kind of pH sensor based on redox graphene and preparation method thereof and utilize this sensor, mainly be to utilize the self assembly of graphene oxide thin slice to form graphene oxide film, and have the sense film of perfecting electric conductivity by heat reduction formation.
Background technology
To the Research of Dynamic Analysis of information exchanging process in the life system, often need to understand pH small in the biosome living environment change with and the real time altering situation that changes along with the life entity survival condition of numerical value.Therefore, need that development is a kind of to have a high sensitivity, quick, real-time, the simple technique that can carry out performance analysis and research to the pH of the environment at life entity place.
The method of at present pH detection mainly contains: indicator method, chemical analysis and potential method etc.Indicator method is the chromogenic reaction of utilizing solution and test paper, compares with the standard test paper afterwards.There is very large error in this method.Chemical analysis operation more complicated.The current potential rule is to utilize galvanic principles that chemical energy is converted into electric energy, and its degree of accuracy is high, and is easy to operate, is now widely used method, and for this less situation of institute's test sample, there is not advantage in the current potential rule.
The people such as Peng Chen, Yasuhide Ohno have studied the response of Graphene to the pH value, and discovery pH value and the electricity of surveying have been led good linear relationship.But response speed is not quite desirable.Response time needed about half a minute.Graphene oxide is the oxide of Graphene, and with respect to Graphene, it exists defective and abundant chemical group, so chemical activity is high.The abundant functional group of graphene oxide has increased its functional diversity, for chemical sensitisation has increased possibility.Graphene oxide is nonconducting originally, but the redox graphene through forming after the reduction has partial reduction to form large π key, so can be so that its electric conductivity improves several orders of magnitude.Since its electrology characteristic, chemical characteristic and stability, and redox graphene has very large advantage in bio-sensing and chemical sensitisation.
Summary of the invention
Based on the problems referred to above, we have proposed a kind of method of novel detection pH value here, mainly are to utilize graphene oxide film that autonomous dress forms as the interface of sensing.It is transferred between the electrode with magnetron sputtering or electron beam evaporation plating, by the thermal treatment reduction, form the oxidation graphene film with excellent conductive performance.Because (COOH) etc. functional group can ionize out hydrogen ion (H with carboxyl on the redox graphene
+ ), along with solution alkalescence strengthens hydroxide ion (OH
-) increase the H that ionizes out
+Increase, so the conduction electric charge increases on the interface, namely electricity is led increase.On the contrary, if solution acidic increases, then electricity is led and is reduced.This method changes its electrology characteristic by the interaction of ion and redox graphene surface functional group, and the variation of electrology characteristic can detect by the semiconductor parameter instrument.This sensor, simple to operate, and be quick on the draw, sampling quantity is little.In addition, in conjunction with the semiconductor parameter instrument, can also measure electric current along with the variation of time, and then obtain the situation of change of pH value, the dynamic process that can be applicable to the biological or chemical reaction detects.
The purpose of this invention is to provide a kind of simple to operate, response rapidly, highly sensitive pH detection method.The pH that this pH sensor can detect measured matter over time.
Technical scheme of the present invention utilizes the self assembly of graphene oxide thin slice Hydrogenbond to form graphene oxide film; Then it is transferred to the SiO that has with magnetron sputtering or electron beam evaporation plating electrode
2On/Si the substrate, through heat treated, graphene oxide is reduced to redox graphene, makes a groove along the oxidation graphene film edge with insulating polymers such as PMMA subsequently, consist of a pH sensor.
The present invention is by the following technical solutions:
The first step: with natural graphite powder potassium permanganate (KMnO
4), sodium nitrate (NaNO
3) and 98% concentrated sulphuric acid be oxidized to graphite oxide, form the graphene oxide thin slice through the ultrasonic processing of 30min again, then allow the graphene oxide thin slice form graphene oxide film by the Hydrogenbond self assembly;
Second step: with SiO
2/ Si silicon substrate dries up with nitrogen after passing through successively acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning, covers mask plate, utilizes magnetron sputtering at SiO
2Sputter a layer thickness is the Ag film of 200 ~ 300 nanometers on the/Si substrate;
The 3rd step: utilize silicon chip that the graphene oxide film that is suspended in solution surface is transferred to and clean decon in the distilled water, transfer to again between the silver electrode;
The 4th step: the sample of above preparation is put into clean reactor, use the nitrogen deaeration, the reactor with sealing is put in the drying box subsequently, and 180 ℃ were heated 5 hours, takes out after its cooling;
The 5th step: polymethylmethacrylate (PMMA) is dissolved in the acetone soln, and ultrasonic one-tenth colloidal sol disperse system is applied to it around graphene oxide film, forms groove after the acetone volatilization, has just consisted of complete pH sensor;
The 6th step: get 286.5mg sodium hydrogen phosphate crystal (Na2HPO
412H2O) with 1435.3mg biphosphate sodium crystal (NaH2PO
42H2O) be dissolved in the 50ml distilled water and be configured to pH=5.8, solubility is the phosphate buffered solution of 0.2mol/L; Get 3391.6mg sodium hydrogen phosphate crystal (Na2HPO
412H2O) with 82.7mg biphosphate sodium crystal (NaH2PO
42H2O) be dissolved in the 50ml distilled water and be configured to pH=8.0, solubility is the phosphate buffered solution of 0.2mol/L.
The 7th step: sensor is connected on the semiconductor parameter instrument test platform, and it is 1V that bias voltage is set, and measures the change curve of electric current along with the time;
The 8th step: the pH=5.8 that at first drips 6 μ L in the groove of polymethylmethacrylate (PMMA) formation, solubility is the phosphate buffered solution of 0.2mol/L, then divide the pH=8.0 that drips 3 μ L for 3 times, solubility is the phosphate buffered solution of 0.2mol/L, then measures its electrology characteristic with the semiconductor parameter instrument.
Compared with prior art, the present invention has the following advantages:
1. the present invention has used the synthetic graphene oxide of chemical method, can produce in a large number.
2. among the present invention, utilize the heat-treating methods redox graphene, method of reducing is simple, and desired experiment condition is not high, is conducive to industrialization.
3. among the present invention, utilize the heat-treating methods redox graphene after, contacting by Schottky contacts between graphene oxide and the electrode becomes Ohmic contact, and electric conductivity has the lifting of several orders of magnitude.
4. among the present invention, PMMA is dissolved in ultrasonic formation colloidal dispersion system in the acetone, forms groove around can directly being coated in graphene oxide.Need not etching and mask, and can prevent that PMMA from covering redox graphene.
5. the present invention has utilized the functional group on the redox graphene, and it as sensing interface, has been avoided complicated chemical modification process.
6. the present invention uses the semiconductor parameter instrument to detect the variation of the electrical parameter on redox graphene surface.In conjunction with the function of semiconductor parameter instrument, can dynamically record the variation of pH value.The dynamic process that can be applied to the biological or chemical reaction detects.
The present invention for the response time of pH within 25s, improve a lot with respect to the response speed of Graphene.
Description of drawings
Fig. 1 is the graphene oxide film SEM figure that utilizes self assembly;
Fig. 2 (a-c) is based on the pH sensor preparation flow figure of redox graphene;
Fig. 3 (a) is the I-V curve of graphene oxide before the heat treated; The I-V curve of Fig. 3 (b) heat reduction rear oxidation Graphene;
Fig. 4 is that in the gradually increase process of pH value, sensor current is along with the change curve of time after dripping acid-base solution.
Embodiment
Embodiments of the invention are only take the redox graphene pH sensor for preparing silver electrode with magnetron sputtering method as example, but are not limited to the particular content of embodiment.
The present invention prepare silver electrode redox graphene pH sensor method by the following technical solutions:
The first step: with natural graphite powder potassium permanganate (KMnO
4), sodium nitrate (NaNO
3) and 98% concentrated sulphuric acid be oxidized to graphite oxide, form the graphene oxide thin slice through the ultrasonic processing of 30min again, then allow the graphene oxide thin slice form the graphene oxide film (see figure 1) by the Hydrogenbond self assembly.
Second step: with the SiO of 1cm*1.5cm
2/ Si silicon substrate dries up with nitrogen after passing through successively acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning 20min, covers mask plate, utilizes magnetron sputtering at SiO
2Sputter a layer thickness is about the Ag film of 300 nanometers on the/Si substrate, and sputtering time is 20 minutes, and power is 100W, air pressure 2Pa, logical argon gas (Ar) 55.5sccm.
The 3rd step: utilize silicon chip that the graphene oxide film that is suspended in solution surface is transferred to and clean decon in the distilled water, transfer to again between the silver electrode, behind natural air drying under its room temperature, measure its I-V curve and (see Fig. 3 a).Graphene oxide is in state of insulation at this moment.
The 4th step: the sample of above preparation is put into clean reactor.Use the nitrogen deaeration, the reactor with sealing is put in the drying box subsequently, and 180 ℃ were heated 5 hours, takes out after its cooling.I-V curve (seeing Fig. 3 b) behind the measurement heat reduction.
The 5th step: polymethylmethacrylate (PMMA) is dissolved in the acetone soln, ultrasonic one-tenth colloidal sol disperse system, (in this state, the acetone soln of PMMA can not flow.) it is applied to around the graphene oxide film, form groove after the acetone volatilization, just consisted of complete pH sensor (see figure 2), again measure its I-V curve (seeing Fig. 3 b), improve a lot through the graphene oxide conductive characteristic of heat treated reduction.
The 6th step: get 286.5mg sodium hydrogen phosphate crystal (Na2HPO
412H2O) with 1435.3mg biphosphate sodium crystal (NaH2PO
42H2O) be dissolved in the 50ml distilled water and be configured to pH=5.8, solubility is the phosphate buffered solution of 0.2mol/L; Get 3391.6mg sodium hydrogen phosphate crystal (Na2HPO
412H2O) with 82.7mg biphosphate sodium crystal (NaH2PO
42H2O) be dissolved in the 50ml distilled water and be configured to pH=8.0, solubility is the phosphate buffered solution of 0.2mol/L.
The 7th step: sensor is connected on the semiconductor parameter instrument test platform.It is 1V that bias voltage is set, and measures the change curve (be I-t curve) of electric current along with the time.
The 8th step: at first drip the pH=5.8 of 6 μ L in the groove that forms toward PMMA, solubility is the phosphate buffered solution of 0.2mol/L, then divides the pH=8.0 of 3 dropping 3 μ L, and solubility is the phosphate buffered solution of 0.2mol/L.The variation of observation electric current, in Fig. 4, along with the progressively increase of pH value, the hydrogen ion that the functional group such as carboxyl ionizes out on the redox graphene increases, and the quantity of electric charge increase on the interface is so the electric current that detects also progressively increases.
In addition, in above-mentioned steps, polymethylmethacrylate (PMMA) can be dissolved in the acetone soln, behind the ultrasonic formation collosol state, it is applied to around the graphene oxide film, forms groove after the acetone volatilization, can need not like this to use mask and etching, experimental procedure is simplified.Can also use simultaneously oxidation graphene film as the sensitive materials of induction pH variation, and with the method for annealing graphene oxide be reduced.
The invention is not restricted to top application, in the various possible scopes that are modified in dependent claims, also can be manufactured for other modification of above-mentioned embodiment.Therefore, it is to be understood that the invention is not restricted to disclosed embodiment and its modification and other embodiment intention comprises in the appended claims.Although used concrete term at this, they only be used in general and the narration situation under and unrestriced purpose.
Claims (5)
1. a utilization is characterized in that based on the pH value detection method of the pH sensor of redox graphene:
The first step: with natural graphite powder potassium permanganate (KMnO
4), sodium nitrate (NaNO
3) and 98% concentrated sulphuric acid be oxidized to graphite oxide, form the graphene oxide thin slice through the ultrasonic processing of 30min again, then allow the graphene oxide thin slice form graphene oxide film by the Hydrogenbond self assembly;
Second step: with SiO
2/ Si silicon substrate dries up with nitrogen after passing through successively acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning, covers mask plate, utilizes magnetron sputtering at SiO
2Sputter a layer thickness is the Ag film of 200 ~ 300 nanometers on the/Si substrate;
The 3rd step: utilize silicon chip that the graphene oxide film that is suspended in solution surface is transferred to and clean decon in the distilled water, transfer to again between the silver electrode;
The 4th step: the sample of above preparation is put into clean reactor, use the nitrogen deaeration, the reactor with sealing is put in the drying box subsequently, and 180 ℃ were heated 5 hours, takes out after its cooling;
The 5th step: polymethylmethacrylate (PMMA) is dissolved in the acetone soln, and ultrasonic one-tenth colloidal sol disperse system is applied to it around graphene oxide film, forms groove after the acetone volatilization, has just consisted of complete pH sensor;
The 6th step: get 286.5mg sodium hydrogen phosphate crystal (Na2HPO
412H2O) with 1435.3mg biphosphate sodium crystal (NaH2PO
42H2O) be dissolved in the 50ml distilled water and be configured to pH=5.8, solubility is the phosphate buffered solution of 0.2mol/L; Get 3391.6mg sodium hydrogen phosphate crystal (Na2HPO
412H2O) with 82.7mg biphosphate sodium crystal (NaH2PO
42H2O) be dissolved in the 50ml distilled water and be configured to pH=8.0, solubility is the phosphate buffered solution of 0.2mol/L;
The 7th step: sensor is connected on the semiconductor parameter instrument test platform, and it is 1V that bias voltage is set, and measures the change curve of electric current along with the time;
The 8th step: the pH=5.8 that at first drips 6 μ L in the groove of polymethylmethacrylate (PMMA) formation, solubility is the phosphate buffered solution of 0.2mol/L, then divide the pH=8.0 that drips 3 μ L for 3 times, solubility is the phosphate buffered solution of 0.2mol/L, then measures its electrology characteristic with the semiconductor parameter instrument.
2. the pH value detection method of the pH sensor based on redox graphene according to claim 1, it is characterized in that polymethylmethacrylate (PMMA) is dissolved in the acetone soln, behind the ultrasonic formation collosol state, it is applied to around the graphene oxide film, form groove after the acetone volatilization, can need not like this to use mask and etching, experimental procedure is simplified.
3. the pH value detection method of the pH sensor based on redox graphene according to claim 1 is characterized in that the sensitive materials that change as induction pH with oxidation graphene film.
4. the pH value detection method of the pH sensor based on redox graphene according to claim 1 is characterized in that with heat-treating methods graphene oxide being reduced.
5. one kind by the pH sensor based on redox graphene produced in the pH value detection method claimed in claim 1.
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| CN103585004A (en) * | 2013-11-19 | 2014-02-19 | 湖北中医药大学 | Nanometer sensing needle and manufacturing method thereof |
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| CN104291323A (en) * | 2014-09-04 | 2015-01-21 | 天津师范大学 | Preparation method for upconversion graphene oxide and application in indicating pH of water sample |
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| CN103675061A (en) * | 2013-12-16 | 2014-03-26 | 南京市第二医院 | Anatase type TiO2 nano particle based pH sensor and pH value detection method |
| CN104810426A (en) * | 2014-01-26 | 2015-07-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-driven light detector and preparation method thereof |
| CN104291323A (en) * | 2014-09-04 | 2015-01-21 | 天津师范大学 | Preparation method for upconversion graphene oxide and application in indicating pH of water sample |
| CN104291323B (en) * | 2014-09-04 | 2016-08-17 | 天津师范大学 | The preparation method of a kind of upper conversion graphene oxide and water sample indicate the application of pH |
| CN104914150A (en) * | 2015-06-15 | 2015-09-16 | 上海交通大学 | Graphene/polyaniline composite membrane based pH detecting electrode |
| CN104914150B (en) * | 2015-06-15 | 2018-11-20 | 上海交通大学 | A kind of pH detecting electrode based on graphene/polyaniline composite membrane |
| CN105842313B (en) * | 2016-05-09 | 2018-06-26 | 江苏大学 | A kind of graphene-based bionical pH sensors of micro-nano texturing and preparation method thereof |
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| US10690615B2 (en) | 2016-05-09 | 2020-06-23 | Jiangsu University | Micro-nano textured graphene-based bionic pH sensor and preparation method therefor |
| WO2018018689A1 (en) * | 2016-07-29 | 2018-02-01 | 江苏大学 | Super-hydrophilic bionic sensor for moisture content of matrices and preparation method therefor |
| CN106814117A (en) * | 2017-01-22 | 2017-06-09 | 河北科技大学 | PMo12‑SiO2The preparation method of rGO composites and its methods and applications of modified electrode |
| CN109724752A (en) * | 2017-10-27 | 2019-05-07 | 海成帝爱斯株式会社 | Leak detection system and leakage detection method |
| CN109724752B (en) * | 2017-10-27 | 2021-01-15 | 海成帝爱斯株式会社 | Leak detection system and leak detection method |
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| CN113125523B (en) * | 2021-04-19 | 2023-08-11 | 苏州大学 | Humidity sensor based on PAAm flexible hydrogel and preparation method thereof |
| CN114076787A (en) * | 2021-11-24 | 2022-02-22 | 山东省科学院生物研究所 | Polymer volt-ampere type pH electrode and preparation method and application thereof |
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Application publication date: 20131023 |